WO2009118348A2 - Polymérisation d’oxyde d’hexafluoropropylène - Google Patents

Polymérisation d’oxyde d’hexafluoropropylène Download PDF

Info

Publication number
WO2009118348A2
WO2009118348A2 PCT/EP2009/053532 EP2009053532W WO2009118348A2 WO 2009118348 A2 WO2009118348 A2 WO 2009118348A2 EP 2009053532 W EP2009053532 W EP 2009053532W WO 2009118348 A2 WO2009118348 A2 WO 2009118348A2
Authority
WO
WIPO (PCT)
Prior art keywords
hfpo
less
oligomerization
process according
solvent
Prior art date
Application number
PCT/EP2009/053532
Other languages
English (en)
Other versions
WO2009118348A3 (fr
Inventor
Bernard Danner
Original Assignee
Clariant International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Priority to EP09724073A priority Critical patent/EP2262847A2/fr
Priority to BRPI0910054A priority patent/BRPI0910054A2/pt
Priority to CA2719725A priority patent/CA2719725A1/fr
Priority to JP2011501223A priority patent/JP5774470B2/ja
Priority to CN200980110755.4A priority patent/CN101990550B/zh
Priority to US12/934,379 priority patent/US8653229B2/en
Priority to MX2010010592A priority patent/MX2010010592A/es
Publication of WO2009118348A2 publication Critical patent/WO2009118348A2/fr
Publication of WO2009118348A3 publication Critical patent/WO2009118348A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine

Definitions

  • the present invention relates to the anionic polymerization of hexafluoropropylene oxide (HFPO).
  • HFPO hexafluoropropylene oxide
  • the present invention relates to a polymerization of HFPO that yields a desired degree of polymerization combined with a low amount of low molecular weight oligomers of HFPO.
  • Low molecular weight oligomers are those oligomers having a degree of polymerization of 4 or less.
  • WO2006093885 relates to a process for polymerizing a mixture of HFPO and HFP in the presence of an aprotic organic solvent using KF as a catalyst. Disadvantage of all these processes is the use of HFP which is difficult to recycle due to the low boiling point ( -28 °C ) .
  • PALETA ET AL "Radical additions to fluoro-olefins - photochemical mono- fluoroalkylation and sequential bis-fiuoroalkylation of Oxolane", JOURNAL OF FLUORINE CHEMISTRY, vol. 80, 1996, pages 125-134 relates to the polymerization of HFPO with KF and diglyme (diethyl eneglycol dimethyl ether) in the presence of hexafluoropropene ( HFP ) and ethyl fluoro oxalate resulting in oligomers ranging from the dimer to the heptamer.
  • HFP hexafluoropropene
  • US 2004/0116742 relates to a reaction wherein HFPO is condensed with a low molecular acid fluorid and almost 100% of the product is the 1 :1 and the 1 :2 addition product.
  • the present invention provides a process for the oligomerization of hexafluoropropylene oxiyde (HFPO) to get oligomers in which the sum of the dimers, trimers, tetramers, pentamers and hexamers represents less than 20% ,preferably less than 15%, most preferred less than 10% of the weight of the fully consumed HFPO, the remaining oligomers having an average molecular weight between 1100 and 4000 g/mol, which comprises contacting HFPO at a temperature between -30 0 C to + 50 0 C with a catalytic system is formed from potassium fluoride (KF) with a glycol ether in the presence of a perfluorinated or partially fluorinated, non chlorinated, saturated, aliphatic or aromatic hydrocarbon with more than 3 and less than 12 carbon atoms and optionally a polar group at a pressure of less than 3 bars by controlled monomer addition or by adding the monomer in one or two portions
  • KF potassium fluoride
  • the present invention provides a process for the oligomerization of hexafluoropropylene oxide (HFPO) in which the sum of the dimers, trimers, tetramers, pentamers and hexamers represents less than 20%, preferably less than 15%, most preferred less than 10% of the weight of the polymerized HFPO, the oligomer other than the dimers, trimers, tetramers, pentamers and hexamers (the remaining oligomers) having an average molecular weight between 1100 and 4000 g/mol, characterized in that the process comprises the steps of contacting hexafluoropropylene oxide (HFPO) at a temperature between -30 0 C to + 50 0 C with a catalytic system is formed from potassium fluoride (KF) with a glycol ether in the presence of a solvent which is selected from perfluorinated saturated aliphatic or aromatic hydrocarbon with more than 3 and less than 12 C-atoms and optionally the solvent comprises
  • the process of the present invention is carried out in the absence of hexafluoropropylene (HFP).
  • HFP hexafluoropropylene
  • the catalytic system is formed from potassium fluoride (KF) with a glycol ether, wherein preferably the glycol ethers are selected from diethyleneglycol-dimethylether, triethyleneglycol-dimethylether, tetraethyleneglycol-dimethylether and pentaethyleneglycol-dimethylether.
  • KF potassium fluoride
  • the low molecular weight volatile oligomers are distilled out of the resulting mixture of oligomers after the polymerization.
  • the low molecular weight volatile oligomers are distilled out of the resulting mixture of oligomers after transforming the formed oligomers into the corresponding ester.
  • the solvent is not fully perfluorinated.
  • the oligomerization is carried out in the presence of a solvent containing an aromatic group, anether or an ester group.
  • the oligomerization is carried out at temperatures between -20 0 C and + 20 0 C.
  • the oligomerization is carried out by controlled monomer addition at a pressure of less than 2 bars, more preferably less than 1.8 bar.
  • the oligomerization can be carried out in the presence of an additional polar, non fluorinated solvent.
  • the glymes (di-, tri- , tetra - or penta - ethyleneglycol- dimethylether) are a part of the catalytic system.
  • the ratio of HFPO to KF (by weight) varies from 20 to 140 and ranges preferably in the continuous process from 20 to 60, more preferably from 30 to 50.
  • Controlled Monomer Addition means that the addition is steady with a relatively constant flow of HFPO (continuous feeding) and the temperature and the pressure are also kept as constant as possible (constant pressure means plus-minus 10 0 C, preferably plus-minus 5°C, more preferably plus-minus 2°C; the pressure shall not raise over 3 preferably not over 2 more preferably not over 1.8 bar and the pressure in the reaction vessel shall not change more than 30% preferably not more than 20%) by adjusting the temperature of the cooling jacket, respectively by cooling the reaction vessel.
  • the preferred method of regulation of the temperature and the pressure is the regulation of the addition rate of the HFPO. If the pressure or the temperature is rising over the set limits, the addition rate of HFPO is reduced (but preferably the addition of HFPO is not totally stopped), and if the temperature or the pressure is falling below the set limit, the addition rate of the HFPO is increased.
  • the preferred monomer addition method is the controlled monomer addition thus the monomer is continuously fed into the vessel.
  • the vessel When starting with the addition of the HFPO, the vessel is kept under vacuum, and during the addition of the HFPO the pressure and the temperature is raising to the level on which the reaction is carried out and kept at this level.
  • the oligomerisation of the remaining HFPO in the reactor makes that the pressure is sinking and at the end a vacuum is built up. The lower the HFPO concentration in the reactor is remaining the lower is the pressure in the reactor.
  • the oligomerization is carried out with a weight ratio of the di-, tri- or tetraethyleneglycol-dimethylether (glyme) to potassium fluoride ranging between 1.0 and 10.0.
  • the oligomerization is carried out with a weight ratio of the perfluorinated solvent and the di-, tri- or tetraethyleneglycol-dimethylether ranging between 1 and 25.
  • Possible solvents for the process of the present invention are CF3CH2OCH2CF3;
  • Decafluorocyclohexane Difluorobenzene, Trifluorobenzene, Perfluoro-n-pentane, Perfluorohexane, Perfluoromethylcyclohexane, Perfluoro-n-butane, Perfiuoromethyldecalin, H(CF 2 ) 4 H ,H(CF 2 ) 6 H ,CF 3 CHFCHFCF 2 CF 3 , Hexafluorocyclobutane.
  • Possible fluorinated solvent with nitrilogroups are 3,5-Bis (trifluoromethyl)benzonitrile, Difluorobenzonitrile or CF 3 CF 2 CF 2 CN, HCF 2 CFHOCF 2 CF(CF 3 )CN.
  • Preferred solvents are perfluorinated or fluorinated solvents. Preference is given to fluorinated resp. perfluorinated solvents with more than 3 and less than 12 Carbon atoms.
  • the more preferred solvents are selected from the group of 1,3- bistrifluoromethylbenzene, perfluoro-2-n-butyl-tetrahydrofurane, 1,1,1,3,3,- pentafluorobutane, l-(propoxy)heptafluopropane, l-(methoxy)nonafluorobutane, 1- (ethoxy)-nonafluorobutane, 3-ethoxy-l , 1 ,1 ,2,3,4,4,5,5,6,6,6,-dodecafluoro-2- trifluoromethyl-hexane, bis(2,2,2-trifluoroethylether ), 1 -methoxy- 1 , 1 ,2,3 ,3 ,3 ,- hexafluoro
  • Especially preferred solvents are nonafluorobutyl-methylether, 1,3-bis- (trifluoromethyl)-benzene and 1,1,1,3,3-pentafluorobutane.
  • a single fluorinated solvent or mixtures of different fluorinated solvents can also be used.
  • non fluorinated solvents like acetonitrile, 1,3-dicyano-propane, 1,4-dicyano- butane can be present as cosolvents. Preferably, there are no non fluorinated solvents present.
  • the obtained polymeric oligo(HFPO) ⁇ -terminated (omega- terminated; see IUPAC-rule 3-AA-2.2.1) acid fluoride is generally converted into an ester by reaction with an alcohol , optionally in the presence of a base in order to neutralize the generated HF.
  • an alcohol optionally in the presence of a base in order to neutralize the generated HF.
  • methanol in excess is used together with a tertiary amine to convert the acid fluoride into the methyl ester.
  • Low molecular weight oligomeric methylesters can then be separated from the higher oligomeric HFPO - methylesters and quantified (weight) by distillation (under vacuum).
  • the equivalent weight of 1 COOCH3 group of the distillation residue is determined by reacting the polymeric ester with an amine in excess and titration of the unreacted amine. This equivalent weight is close to the average molecular weight which can be determined by Gel Permeation Chromatography (GPC or SEC). GC can also be used to check the absence of peaks of low molecular weight species. The amount of distillation residue compared to the amount of introduced HFPO in combination with the GC analysis of the residue and the distillate gives the amount of low molecular weight oligomers formed during polymerization.
  • the resulting oligomers according to the present invention have a viscosity of 70 to 8000 mPas preferably 300 to 3000 mPas when measured with a Brookf ⁇ eld® rotation viscosimeter using the spindle number 3 at 23 0 C.
  • a dry, stainless-steel pressure-vessel equipped with a stirrer, thermometer, a heating and cooling jacket, a gas inlet tube for nitrogen or hexafluoropropyleneoxyde (HFPO), a connection to a vacuum line and the possibilty to connect a side arm fitted with a condenser and optionally a receiver, tetraethyleneglycoldimethylether (tetraglyme) and the catalyst are loaded under agitation and heated up to 100 0 C under vacuum to remove traces of water. After cooling down to -15°C the HFPO is released into the vacuum, optionally together with the perfluorinated or partially fluorinated solvent is added.
  • HFPO hexafluoropropyleneoxyde
  • the temperature is adjusted to the desired value chosen for the anionic ring-opening polymerisation and the addition of HFPO is started with a high speed of agitation to get a good distribution and small size of the gas bubbles in the liquid.
  • the pressure in the vessel is adjusted to 1.2 to 1.8 bar by setting the speed of addition.
  • the HFPO addition is stopped and after vacuum (200 to 700 mbar) was obtained in the polymerization reactor the temperature is slowly increased to 20 0 C, the perfluorinated solvent is distillated under vacuum and the distillation residue is poured on dry methanol with agitation. After the separation of the polymer and methanol phases, the liquid viscous polymer phase is washed several times with methanol in order to remove the formed HF and traces of the catalyst (KF and tetraethyleneglycoldimethylether). The obtained polymeric HFPO methylester is then distillated in order to remove low molecular weight species. Distillation is run at 160 0 C and approx. 1 mm Hg pressure (vacuum). The yield is the percentage of polymeric HFPO methylester (residue of the distillation) related to the quantity of introduced (consumed) monomeric HFPO.
  • the obtained oligomeric HFPO methyl ester may contain small amounts of KF which is filtered off.
  • the product is a clear oil with a viscosity which depends on the polymerisation degree.
  • n signifies the oligomerisation degree
  • n signifies the oligomerisation degree
  • a pressure vessel is charged with 1,75 g KF followed by the addition of 10,0 g tetraglyme and 11,8 g acetonitrile. Then the reactor is fluxed with nitrogen and cooled to -10 0 C.
  • a first step approx. 25 g of HFPO are introduced into the pressure vessel and stirred during some hours in order to be converted to soluble initiator compound.
  • the second step is started with the addition of 206,7 g l,3-bis(trifluormethyl)-benzene and the addition at -10 0 C during 2h at a pressure of 0,7 bar of 210,0 g of HFPO.

Abstract

La présente invention concerne un procédé d’oligomérisation d’oxyde d’hexafluoropropylène (HFPO) dans lequel la somme des dimères, trimères, tétramères, pentamères et hexamères représente moins de 20 % en poids du HFPO polymérisé, les oligomères autres que les dimères, trimères, tétramères, pentamères et hexamères (les oligomères restants) ayant un poids moléculaire moyen compris entre 1100 et 4000 g/mole, caractérisé en ce que le procédé comprend les étapes consistant à mettre en contact de l’oxyde d’hexafluoropropylène (HFPO) à une température comprise entre ‑30 °C et +50 °C avec un système de catalyseur choisi parmi le fluorure de potassium et l’éther diméthylique de di-, tri- ou tétraéthylèneglycol en présence d’un solvant qui est choisi parmi un hydrocarbure aliphatique ou aromatique perfluoré avec plus de 3 et moins de 12 atomes de C et facultativement un groupe polaire mais ne comprenant pas de chlore ou de brome, un hydrocarbure aliphatique ou aromatique partiellement fluoré avec plus de 3 et moins de 12 atomes de C et facultativement un groupe polaire mais ne comprenant pas de chlore ou de brome à une pression de moins de 3 bars par ajout de monomère contrôlé par alimentation continue ou par ajout du monomère en une ou deux portions (ajouts).
PCT/EP2009/053532 2008-03-28 2009-03-25 Polymérisation d’oxyde d’hexafluoropropylène WO2009118348A2 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP09724073A EP2262847A2 (fr) 2008-03-28 2009-03-25 Polymérisation de l'oxyde d'hexafluoropropylène
BRPI0910054A BRPI0910054A2 (pt) 2008-03-28 2009-03-25 polimerização de óxido de hexaflúor-propileno
CA2719725A CA2719725A1 (fr) 2008-03-28 2009-03-25 Polymerisation d'oxyde d'hexafluoropropylene
JP2011501223A JP5774470B2 (ja) 2008-03-28 2009-03-25 ヘキサフルオロプロピレンオキシドの重合
CN200980110755.4A CN101990550B (zh) 2008-03-28 2009-03-25 六氟环氧丙烷的聚合
US12/934,379 US8653229B2 (en) 2008-03-28 2009-03-25 Polymerisation of hexafluoropropylene oxide
MX2010010592A MX2010010592A (es) 2008-03-28 2009-03-25 Polimerizacion de oxido de hexafluoropropileno.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08290293 2008-03-28
EP08290293.3 2008-03-28
EP08290489.7 2008-05-28
EP08290489 2008-05-28

Publications (2)

Publication Number Publication Date
WO2009118348A2 true WO2009118348A2 (fr) 2009-10-01
WO2009118348A3 WO2009118348A3 (fr) 2010-06-10

Family

ID=41051153

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/053532 WO2009118348A2 (fr) 2008-03-28 2009-03-25 Polymérisation d’oxyde d’hexafluoropropylène

Country Status (11)

Country Link
US (1) US8653229B2 (fr)
EP (1) EP2262847A2 (fr)
JP (1) JP5774470B2 (fr)
KR (1) KR20100135279A (fr)
CN (1) CN101990550B (fr)
AR (1) AR073635A1 (fr)
BR (1) BRPI0910054A2 (fr)
CA (1) CA2719725A1 (fr)
CL (1) CL2009000749A1 (fr)
MX (1) MX2010010592A (fr)
WO (1) WO2009118348A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2607397A1 (fr) 2011-12-21 2013-06-26 Clariant International Ltd. Composition fluorochimique et usage correspondant

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103788363A (zh) * 2013-12-25 2014-05-14 上海艾肯化工科技有限公司 一种制备高分子量全氟聚醚的方法
CN108251895A (zh) * 2016-12-29 2018-07-06 江苏鲁汶仪器有限公司 一种氟化氢气相腐蚀设备及方法
CN109485560B (zh) * 2018-11-27 2021-07-09 湖南有色郴州氟化学有限公司 一种选择性合成六氟环氧丙烷低聚物的方法
CN111972413B (zh) * 2020-08-05 2023-05-09 东莞东阳光科研发有限公司 一种过氧化氢消毒组合物及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3322826A (en) * 1962-04-11 1967-05-30 Du Pont Polymerization of hexafluoropropylene epoxide
GB1341975A (en) * 1970-09-22 1973-12-25 Du Pont Fluorine-containing polymers
EP0151877A2 (fr) * 1983-12-27 1985-08-21 Minnesota Mining And Manufacturing Company Oligmères et polymères de perfluoro-polyéthers
US5399754A (en) * 1993-04-26 1995-03-21 Shin-Etsu Chemical Co., Ltd. Process for producing perfluorocarboxylic acid fluoride
WO2004060849A1 (fr) * 2002-12-17 2004-07-22 3M Innovative Properties Company Reaction selective d'oxyde d'hexafluoropropylene avec des fluorures de perfluoroacyle
EP1698650A1 (fr) * 2005-03-02 2006-09-06 3M Innovative Properties Company Polymérisation de l'oxyde d'hexafluoropropylène

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0725875B2 (ja) 1987-02-05 1995-03-22 株式会社トクヤマ フルオロポリエ−テルの製造方法
JPH0297526A (ja) * 1988-10-03 1990-04-10 Asahi Chem Ind Co Ltd 高純度二官能性オリゴマーの取得法
JP3314634B2 (ja) * 1996-10-02 2002-08-12 信越化学工業株式会社 ヘキサフロロプロペンオキシドの重合方法
JP2947264B1 (ja) * 1998-04-01 1999-09-13 信越化学工業株式会社 ヘキサフロロプロペンオキシドの重合方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3322826A (en) * 1962-04-11 1967-05-30 Du Pont Polymerization of hexafluoropropylene epoxide
GB1341975A (en) * 1970-09-22 1973-12-25 Du Pont Fluorine-containing polymers
EP0151877A2 (fr) * 1983-12-27 1985-08-21 Minnesota Mining And Manufacturing Company Oligmères et polymères de perfluoro-polyéthers
US5399754A (en) * 1993-04-26 1995-03-21 Shin-Etsu Chemical Co., Ltd. Process for producing perfluorocarboxylic acid fluoride
WO2004060849A1 (fr) * 2002-12-17 2004-07-22 3M Innovative Properties Company Reaction selective d'oxyde d'hexafluoropropylene avec des fluorures de perfluoroacyle
EP1698650A1 (fr) * 2005-03-02 2006-09-06 3M Innovative Properties Company Polymérisation de l'oxyde d'hexafluoropropylène

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198837 Thomson Scientific, London, GB; AN 1988-261833 XP002574082 & JP 63 191825 A (TOKUYAMA SODA KK) 9 August 1988 (1988-08-09) *
E. MEISSNER, E.A.: "Oligomerization of hexafluoropropylene oxide in the presence of alkali metal halides" POLISH JOURNAL OF CHEMICAL TECHNOLOGY, vol. 9, no. 3, 2007, pages 95-97, XP008111811 *
HILL J T: "Polymers from hexafluoropropylene oxide" JOURNAL OF MACROMOLECULAR SCIENCE A. PURE AND APPLIEDCHEMISTRY, MARCEL DEKKER, US, vol. 8, no. 3, 1 January 1974 (1974-01-01), pages 499-520, XP008092019 ISSN: 1060-1325 *
PALETA O ET AL: "Radical additions to fluoro-olefins. photochemical mono-fluoroalkylation and sequential bis-fluoroalkylation of oxolane" JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, NL, vol. 80, 1 January 1996 (1996-01-01), pages 125-134, XP004071320 ISSN: 0022-1139 cited in the application *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2607397A1 (fr) 2011-12-21 2013-06-26 Clariant International Ltd. Composition fluorochimique et usage correspondant
WO2013091804A1 (fr) 2011-12-21 2013-06-27 Clariant International Ltd Composition de produit chimique fluoré et son utilisation

Also Published As

Publication number Publication date
CN101990550A (zh) 2011-03-23
JP5774470B2 (ja) 2015-09-09
MX2010010592A (es) 2010-10-20
EP2262847A2 (fr) 2010-12-22
US8653229B2 (en) 2014-02-18
CN101990550B (zh) 2014-03-12
BRPI0910054A2 (pt) 2015-12-29
WO2009118348A3 (fr) 2010-06-10
CA2719725A1 (fr) 2009-10-01
US20110092665A1 (en) 2011-04-21
KR20100135279A (ko) 2010-12-24
AR073635A1 (es) 2010-11-24
CL2009000749A1 (es) 2009-05-08
JP2011515552A (ja) 2011-05-19

Similar Documents

Publication Publication Date Title
RU2144044C1 (ru) Фторированные производные бисвинилоксиметана (варианты), полимеры и сополимеры на их основе
US8653229B2 (en) Polymerisation of hexafluoropropylene oxide
JP2945693B2 (ja) 液相フツ素置換
US8008523B2 (en) Process for preparing high purity monocarboxylic perfluoropolyethers
JP4285000B2 (ja) 含フッ素エステル、含フッ素アシルフルオリドおよび含フッ素ビニルエーテルの製造方法
US5539059A (en) Perfluorinated polyethers
US6335408B1 (en) Copolymers of perfluorodioxoles
KR20160048083A (ko) 함불소 화합물의 제조 방법
KR0164217B1 (ko) 퍼할로겐화된 폴리에테르
US5506309A (en) Perfluorinates polyethers
JP4961656B2 (ja) ペルフルオロアシルフルオリド類の製造方法
US7071272B2 (en) Method for preparing unsaturated compound by pyrolysis reaction
EP1760063A1 (fr) Composé d'éther de vinyle contenant du fluor et procédé servant à produire celui-ci
JPH10158387A (ja) ヘキサフロロプロペンオキシドの重合方法
JP4823410B2 (ja) 含フッ素重合体の製造方法
KR102425264B1 (ko) 높은 전환율을 갖는 헥사플루오로프로필렌 옥사이드 이량체의 제조방법
EP1440994A2 (fr) Procédé pour la préparation de composés carbonyl monofonctionnels perfluorinés
JPWO2002079274A1 (ja) 含フッ素重合体およびその誘導体の製造方法、および含フッ素重合体の誘導体の用途
EP1440993A2 (fr) Procédé pour la préparation de composés carbonyl monofonctionnel perfluorinés
US20100256412A1 (en) Fluorinated polyethers and polyether oils and methods of preparation
JP2002332309A (ja) 含フッ素重合体の製造方法
CA1188849A (fr) Ethers-oxydes perfluorodiglycidyliques
JP2005171054A (ja) フッ素ポリマーの製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980110755.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09724073

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2009724073

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011501223

Country of ref document: JP

Ref document number: 2719725

Country of ref document: CA

Ref document number: MX/A/2010/010592

Country of ref document: MX

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20107024180

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 12934379

Country of ref document: US

ENP Entry into the national phase

Ref document number: PI0910054

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20100924